CN102245664B - Phenol resin for shell molding, process for production of resin, resin-coated sand for shell molding, and molds obtained using same - Google Patents
Phenol resin for shell molding, process for production of resin, resin-coated sand for shell molding, and molds obtained using same Download PDFInfo
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- CN102245664B CN102245664B CN200980149871.7A CN200980149871A CN102245664B CN 102245664 B CN102245664 B CN 102245664B CN 200980149871 A CN200980149871 A CN 200980149871A CN 102245664 B CN102245664 B CN 102245664B
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- shell mould
- aphthols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Abstract
The present invention provides a phenol resin for shell molding, which can advantageously provide molds that produce little tar in casting and that have both low thermal expansion coefficients and high collapsibility; a resin-coated sand obtained using same; and molds obtained using the resin-coated sand. A phenol resin having such useful characteristics is obtained by reacting a phenol component comprising both a phenol and a naphthol with an aldehyde using a divalent metal salt and/or oxalic acid as the reaction catalyst.
Description
Technical field
The present invention relates to shell mould by resol and manufacture method thereof and shell mould with coated sand and use the casting mold of its formation, particularly relate to the growing amount of the thermal decomposition product (hereinafter to be referred as making " tar ") producing in the time of can suppressing to cast and solve thermal expansivity and coated sand that the shell mould of contractility problem obtains with resol and manufacture method thereof, the described resol of use and use it to carry out the casting mold of moulding formation simultaneously.
Background technology
All the time, in shell mould (shell mold) casting, conventionally use following shell casting mold,, use coated sand (hereinafter to be referred as making " RCS ") to carry out hot briquetting to it, form thus the shell casting mold with intended shape, described coated sand is by the solidifying agent such as vulkacit H of resistivity against fire particle (molding sand) and resol (tackiness agent) and use are as required carried out to mixing obtaining.
But, in such casting mold, particularly in the situation that manufacture IC engine cylinder head and so on casting mold cast article, complex-shaped, in using the casting operation of this casting mold, there is the problem that easily causes be full of cracks or slight crack (" slight crack " that be called below, casting mold).In addition, in the process of complex-shapedization that makes casting mold, the tendency that exists venting hole to reduce, therefore, when casting, the generation of the tar (Tar) of Autoadhesive also becomes a serious problem.
Therefore, in order to prevent that casting mold from producing slight crack, to it is generally acknowledged, can reduce the coefficient of thermal expansion of casting mold, increase contractility simultaneously, in patent documentation 1, disclose by using the bisphenols such as dihydroxyphenyl propane or bis-phenol E as binder constituents, anxious coefficient of thermal expansion can be reduced, therefore low heat expansion property can be realized.But, although aforesaid method can fully be eliminated the problem that casting mold produces slight crack, but produced new problem, when casting, the generation quantitative change of tar is many, easily causes casting flaw (for example gas defects).
In addition, following method is disclosed, in patent documentation 2, making to exist in RCS number-average molecular weight is 1500～40000 polyoxyethylene glycol, prevent thus the slight crack (crackle) of casting mold, while still adopting the method, the raising of thermal expansion character and contractility insufficient, remains and is improving space.
On the other hand, in patent documentation 3, disclose by using RCS more effectively to reclaim after the shakeout operation after casting the block as shell, described RCS utilizes and at least uses aphthols to form as the surface of the coated molding sand of the destructive resol of difficulty of phenols manufacture, therefore can realize the shell sand after use regeneration rate raising and also can make the steady quality of reclaimed sand.Line style phenolic resinoid or fusible type phenolic resinoid in described embodiment, have been enumerated, described line style phenolic resinoid or fusible type phenolic resinoid are to use the catalyzer such as hydrochloric acid or ammoniacal liquor, naphthyl alcohol or 2-Naphthol or described naphthols and phenol are reacted with formalin obtain, but in the special resin using described hydrochloric acid as catalyzer, the mould etching problem when safety issue that the vigorous reaction while existing by resin manufacture produces and casting and molding.In addition, in this patent documentation 3, there is no the open phenolic resinoid that oxalic acid obtains as catalyzer and use its RCS obtaining of usining completely, while openly not manufacturing casting mold more completely, become feature problem, casting mold slight crack, tar growing amount.
Patent documentation 1: Japanese kokai publication sho 59-178150 communique
Patent documentation 2: Japanese kokai publication sho 58-119433 communique
Patent documentation 3: Japanese kokai publication sho 63-30144 communique
Summary of the invention
Herein, the present invention be take above-mentioned situation and is completed as background, solution problem of the present invention is to provide a kind of shell mould by resol and manufacture method thereof and uses the RCS that this resol obtains and use above-mentioned RCS to carry out the casting mold that moulding obtains, and described shell mould is conducive to obtain tar growing amount casting mold few, that coefficient of thermal expansion is low and contractility is large when the casting with resol.
In order to solve above-mentioned problem, the inventor etc. conduct in-depth research with resol shell mould, found that by using phenols and aphthols, above-mentioned phenol composition is reacted with aldehydes, use divalent metal salt and/or oxalic acid as its catalysts simultaneously, can obtain having the resol of useful property, particularly utilize RCS that described resol obtains to carry out in casting mold that moulding obtains, be conducive to suppress tar growing amount, and be conducive to realize the characteristic that coefficient of thermal expansion is low and contractility is large, thereby completed the present invention.
That is, in order to solve above-mentioned problem, main points of the present invention are a kind of shell mould resol, it is characterized in that, use divalent metal salt and/or oxalic acid as catalyzer, make phenols and aphthols react with aldehydes and obtain.
It should be noted that, according to shell mould according to the present invention, use one of preferred version of resol, above-mentioned phenols (P) and aphthols (N) are 0.40～0.80 with mol ratio: the F/ (P+N) that reacts of above-mentioned aldehydes (F).
In addition, according to another preferred version of the present invention, as above-mentioned aphthols, can use 1-naphthols or beta naphthal, and then, by quality ratio, preferably the ratio of above-mentioned phenols and described 1-naphthols or beta naphthal is adjusted to 95～50: 5～50.
And then preferred following formation, that is, shell mould of the present invention is 400～1300 by the number-average molecular weight of resol.
Main points of the present invention are also a kind of RCS (coated sand) for shell mould, it is characterized in that, described shell mould RCS is used shell mould as above with the coated resistivity against fire particle of resol and obtains.
In addition, according to shell mould according to the present invention, use one of preferred version of RCS, with respect to the above-mentioned resistivity against fire particle of 100 mass parts, use the above-mentioned resol of 0.2～10 mass parts.
In addition, main points of the present invention are also a kind of casting mold, use shell mould as above to carry out moulding with RCS, and it are heating and curing and obtain.
And then main points of the present invention are also the manufacture method of resol for a kind of shell mould, it is characterized in that, use divalent metal salt and/or oxalic acid as catalyzer, at least a kind of phenols and at least a kind of aphthols are reacted with at least a kind of aldehydes.
According to one of preferred version of the manufacture method of shell mould use resol according to the present invention, with respect to the above-mentioned phenols and the aphthols that amount to 100 mass parts, above-mentioned catalyzer is used with the ratio of 0.01～5 mass parts.
In addition, according to other preferred embodiment of the present invention, above-mentioned divalent metal salt is selected from lead naphthenate, zinc naphthenate, lead acetate, zinc acetate, zinc borate, plumbous oxide and zinc oxide.
According to the shell mould resol of the invention described above, because being makes phenols and aphthols react with aldehydes, and then use at this moment the special catalyst contain divalent metal salt and/or oxalic acid to obtain, so form the coating by this resin formation by the resistivity against fire particle surface in regulation, form shell mould RCS, use this RCS to carry out moulding to casting mold, can be conducive to thus reduce the tar growing amount being produced by above-mentioned casting mold, in addition, the coefficient of thermal expansion of the casting mold meanwhile obtaining is low, and can fully improve the contractility of casting mold, thereby in the time of can solving because of casting, produce the gas defects problem that tar causes simultaneously, and the crackle causing because of the slight crack of casting mold and so on casting flaw problem.And, owing to not containing hydrochloric acid and so on corrodibility composition, so there is following characteristics: can enjoy can be easily and while being manufactured on moulding safely mould there is no the availability in the industries such as advantage of resin of corrosion.
Accompanying drawing explanation
The schematic diagram of the mensuration form that [Fig. 1] is the contractility that represents to measure in embodiment.
Embodiment
As mentioned above, shell mould resol of the present invention is to use the special catalyst contain divalent metal salt and/or oxalic acid, phenols and aphthols is reacted with aldehydes obtain.
, as the phenols of one of reacted constituent as described resol, known material all the time can be enumerated herein, for example, except phenol, the alkylphenols such as cresols, xylenol, p-tert-butylphenol, nonyl phenol can also be enumerated; The polyphenol such as Resorcinol, Bisphenol F, dihydroxyphenyl propane and their mixture etc., can be used separately a kind in them or combine two or more and use.
One of feature of the present invention is to use phenols as above and aphthols as phenol composition, can contribute to thus effectively to improve the characteristic of the resol of gained.It should be noted that, as described aphthols, from being easy to the viewpoints such as acquisition, cost, consider, preferably can use separately 1-naphthols or beta naphthal or use with the form of mixture, wherein, from the aspect of the reactivity excellence with aldehydes, and then consider from the viewpoint of tar growing amount, preferably use 1-naphthols.In addition, by quality ratio, making the ratio of described phenols and aphthols (1-naphthols or beta naphthal) is phenols: aphthols=95～50: 5～50 use, in other words, making aphthols is that 50 quality % of whole phenol compositions are used below.When its reason is that the usage ratio of described aphthols surpasses 50 quality %, during casting, the generation of tar may increase, and in addition, when usage quantity is less than 5 quality %, may bring detrimentally affect to contractility.It should be noted that, from the viewpoint of mould strength, consider phenols: the ratio of aphthols is preferably 90～60: in 10～40 scope, more preferably 90～70: use in 10～30 scope.
In addition, in order to obtain resol of the present invention, as the aldehydes that can react with above-mentioned phenols and aphthols, can enumerate formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, propionic aldehyde etc.Certainly, as described aldehydes, be not limited to the above-mentioned material of enumerating, also can suitably use known raw material apart from the above, and then above-mentioned aldehydes can be used separately, also can use raw material of more than two kinds, without any restriction simultaneously.
In the present invention, in order to make above-mentioned phenols (P) and aphthols (N) react with aldehydes (F) the good resol obtaining as target, recommend the cooperation mol ratio of above-mentioned substance: F/ (P+N), in 0.40～0.80 proportional range, makes described phenols and aphthols react with aldehydes.Wherein, by making described cooperation mol ratio: F/ (P+N), be particularly below 0.75, in particular for below 0.70, can further improve contractility.It should be noted that, by making the value of described F/ (P+N), be more than 0.40, can obtain target resol with sufficient yield, on the other hand, by making the value of described F/ (P+N), be below 0.80, the shell mould forming at the resol that uses gained, with in RCS, can be conducive to improve it is carried out to the intensity of the casting mold of moulding gained.
In addition, one of feature of the present invention is also when above-mentioned phenols and aphthols react with aldehydes, use in divalent metal salt and oxalic acid at least any as specific catalyzer.By using above-mentioned specific catalyzer, can realize growing amount, coefficient of thermal expansion and the contractility of further raising tar.It should be noted that, therefore, as divalent metal salt, such as the metal-salt that can enumerate lead naphthenate, zinc naphthenate, lead acetate, zinc acetate, zinc borate, plumbous oxide, zinc oxide etc. and have divalent metallic element, in addition, can also enumerate and can form an acidic catalyst of above-mentioned metal-salt and the combination of basic catalyst etc.It should be noted that, in above-mentioned specific catalyzer, from the viewpoint of tar growing amount, consider, preferably use oxalic acid.Generally with respect to the phenols and the aphthols that amount to 100 mass parts, above-mentionedly contain ratio that the catalyzer of at least a kind being selected from divalent metal salt and oxalic acid is 0.01～5 mass parts, while being preferably the ratio of 0.05～3 mass parts, be conducive to use.
And then, use when specific catalyzer makes phenols and aphthols react with aldehydes as mentioned above, similarly carry out with the manufacture method of existing resol.The resol obtaining as mentioned above presents the form of solid state or liquid (such as varnish shape or emulsion etc.), for example, under the existence of the solidifying agent such as vulkacit H or curing catalysts or not, by it is heated, present thermoset.It should be noted that, in the present invention, the resol of the number-average molecular weight that preferably use obtains by gel permeation chromatography (GPC) analysis in 400～1300 scopes.When the number-average molecular weight of described resol is too small, the shell mould that the coated resin combination that contains this resin forms is with in RCS, fillibility when moulding is destroyed, possibly cannot guarantee the sufficient intensity of gained casting mold, on the other hand, when the number-average molecular weight of resol is excessive, during heating, the mobility of resin is destroyed, possibly cannot guarantee the sufficient intensity of the casting mold that obtains.
It should be noted that, in the present invention, for above-mentioned resol is used for to shell mould, for the objects such as physical property improvement of casting mold, can in resol, suitably coordinate in advance normally used various additive all the time.Wherein, preferably adopt silane coupling agents such as coordinating γ aminopropyltriethoxy silane or γ-glycidoxypropyltrime,hoxysilane; The lubricants such as ethylenebisstearamide or methylene-bis stearylamide etc.
Therefore, when manufacturing shell mould of the present invention and using RCS, for the further mixing resistivity against fire particle of resol for shell mould as mentioned above.Now, shell mould in RCS of the present invention is to consider that the resin kind used and desired mould strength etc. determine by the use level of resol, therefore do not limit entirely, typically, with respect to 100 mass parts resistivity against fire particles, shell mould by the use level of resol in the scope of 0.2～10 mass parts left and right, preferably in 0.5～8 mass parts, more preferably in the scope of 0.5～5 mass parts.
In addition, for resistivity against fire particle that can be mixing with above-mentioned shell mould use resol, its kind is not particularly limited in the present invention.Base material due to above-mentioned resistivity against fire particle formation casting mold, so can tolerate the resistivity against fire of casting and be suitable for the inorganic particulate that casting mold forms the particle diameter of (moulding) so long as have, can use all the time for any known inorganic particulate of shell-molded.As above-mentioned resistivity against fire particle, except normally used silica sand, can also enumerate special sand such as olivine sand, zircon sand, chromium sand and aluminum oxide sand; The slag class particles such as ferrochrome class slag, ferronickel class slag and converter slag; Naigai Cerabeads (trade(brand)name, ITOCHU Ceratech Co., Ltd.) and so on mullite class Porous particle; Or the regenerated particle that after being cast, reclaiming obtains etc., they can use separately or combine two or more and use.
When manufacturing above-mentioned shell mould and using RCS, its manufacture method is not particularly limited, also can adopt the hot coating method of dry type (dry hot coating), half hot coating method (semi hot coating), cold method with plastic film, and known any method at present such as powder solvent method, but the hot coating method of so-called dry type particularly preferably in the present invention, , in the mixing rolls such as sand muller or high speed sand mill, after resistivity against fire particle through preheating and shell mould is mixing with resin, add vulkacit H (solidifying agent) aqueous solution, by blowing, cooling to make block content disintegration be granular simultaneously, then add calcium stearate (lubricant).
And then, use above-mentioned shell mould with RCS to regulation making molds time, as its heating formative method, be not particularly limited, can advantageously adopt known any method all the time.For example, can obtain as follows casting mold: by above-mentioned RCS by gravity fall mode or be blown into mode etc. and be filled in shaping mould, it is solidified, then, by the casting mold demoulding from above-mentioned shaping mould after solidifying, described shaping mould has to be given the shape space of target casting mold expectation and is heated to 150 ℃～300 ℃.The casting mold obtaining as mentioned above can be conducive to bring into play the effect of above-mentioned excellence.
Embodiment
Below, provide several embodiments of the present invention, be described more specifically the present invention, self-evident the present invention is not subject to any restriction of the content of these embodiment records.In addition, it will be appreciated that as in the present invention, except following examples, and then except above-mentioned concrete description, be also included in various changes that in the scope that does not depart from purport of the present invention, the knowledge based on those skilled in the art is made, correction, improvement etc.
It should be noted that, in below recording, " part " and " % ", as long as no being particularly limited, represents respectively " mass parts " and " quality % ".In addition, the shell mould of manufacture is measured according to following test method with the various characteristics of RCS.
-mensuration of tar growing amount-
4 mould strengths are measured by sample (size: 10mm * 10mm * 60mm) after packing in glass developmental tube (internal diameter 27mm * long 200mm), the measured glass wool of scale (2.5g) inserts near the opening part of developmental tube in advance, makes tar growing amount determinator.Then, said determination device is packed in the tubulose process furnace that temperature in stove remains on 700 ℃, carry out anxious thermal treatment after 6 minutes, take out the cooling normal temperature that is placed to.Afterwards, glass wool is taken out from this determinator, measure its quality.It should be noted that, the growing amount of tar (mg) is the glass wool quality (mg) after anxious heat to be deducted to the glass wool quality (mg) before anxious heat and the value that obtains.
-the contractility evaluation of casting mold-
First, at firing condition: under 250 ℃ * 40 seconds, making is used the casting mold sheet (120mm * 40mm * 5mm) of each RCS as contractility evaluation casting mold, and this casting mold is placed to normal temperature, and cooling.
Next, as shown in Figure 1, after casting mold sheet obtained above is arranged on and supports on platform, its one end to be supported, with heating element (Erema globars), since 200 ℃, slowly heat, make it be warming up to 800 ℃, now, laser displacement gauge is installed in position at the leading section apart from this casting mold sheet (end not being supported) 10mm, directly to Personal Computer input data, situation as displacement, first, by this casting mold sheet is heated, based on expansion behavior and this casting mold bending tablet, soon start afterwards deflection, finally this casting mold sheet is roughly at central part, it is the heating part fracture of heating element.So-called " contractility " herein, with until the maximum deflection that fracture obtains represent, this value is larger, expression casting mold is got over volatility, is rich in flexibility.It should be noted that, when the temperature of heating element is 200 ℃ of left and right, also consider the determination period that next casting mold sheet mensuration starts, carry out this mensuration.
-evaluation of coefficient of thermal expansion-
According to the anxious coefficient of thermal expansion determination test method of recording in JACT test method(s) M-2 coefficient of thermal expansion determination test method, carry out.By at firing temperature: 280 ℃, firing time: the sample of making under the condition of 120 seconds (28.3mm φ * 51mmL, cut about quarter turn) is arranged in the high temperature modification sand test device that temperature in stove is adjusted to 1000 ℃, takes out after 1 minute.Then, according to following calculating formula, by the specimen length before anxious heat and after anxious heat, calculate coefficient of thermal expansion.
Coefficient of thermal expansion (%)={ (suddenly before afterwards hot-anxious heat) specimen length }/(specimen length before anxious heat) * 100
-Production Example 1-
To being provided with in the reaction vessel of thermometer, whipping appts and condenser, drop into 800 parts of phenol, 200 parts of 1-naphthols, 411 part of 47% formalin and 3 parts of oxalic acid.Then, reaction vessel is slowly heated up, arrive after reflux temperature, carry out back flow reaction 90 minutes, further under normal pressure, dewater, be under reduced pressure heated to afterwards 180 ℃, remove unreacted phenol, obtain thus resol 1.The number-average molecular weight of described resol 1 is 850.
-Production Example 2-
Except dropping into 950 parts of phenol, 50 parts of 1-naphthols, 434 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 2 with the same flow process of Production Example 1.
-Production Example 3-
Except dropping into 700 parts of phenol, 300 parts of 1-naphthols, 395 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 3 with the same flow process of Production Example 1.
-Production Example 4-
Except dropping into 500 parts of phenol, 500 parts of 1-naphthols, 253 part of 47% formalin and 2 parts of oxalic acid, according to obtaining resol 4 with the same flow process of Production Example 1.
-Production Example 5-
Except dropping into 800 parts of phenol, 200 parts of beta naphthals, 411 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 5 with the same flow process of Production Example 1.
-Production Example 6-
Except dropping into 800 parts of phenol, 100 parts of 1-naphthols, 100 parts of beta naphthals, 411 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 6 with the same flow process of Production Example 1.
-Production Example 7-
Except dropping into 800 parts of phenol, 200 parts of 1-naphthols, 474 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 7 with the same flow process of Production Example 1.
-Production Example 8-
Except dropping into 800 parts of phenol, 200 parts of 1-naphthols, 411 part of 47% formalin and 2 parts of zinc acetates, according to obtaining resol 8 with the same flow process of Production Example 1.
-Production Example 9-
Except dropping into 800 parts of phenol, 200 parts of 1-naphthols, 411 part of 47% formalin and 2 parts of zinc naphthenates, according to obtaining resol 9 with the same flow process of Production Example 1.
-Production Example 10-
Except dropping into 800 parts of phenol, 200 parts of 1-naphthols, 411 part of 47% formalin and 2 parts of zinc oxide, according to obtaining resol 10 with the same flow process of Production Example 1.
-Production Example 11-
Except dropping into 1000 parts of phenol, 47% formalin and 3 parts of oxalic acid of 441 parts, according to obtaining resol 11 with the same flow process of Production Example 1.
-Production Example 12-
Except dropping into 200 parts of phenol, 800 parts of dihydroxyphenyl propanes (BPA), 234 part of 47% formalin and 3 parts of oxalic acid, according to obtaining resol 12 with the same flow process of Production Example 1.
-Production Example 13-
Except dropping into 800 parts of phenol, 200 parts of 1-naphthols, 411 part of 47% formalin and 1 part of 10% aqueous hydrochloric acid, according to obtaining resol 13 with the same flow process of Production Example 1.
-RCS Production Example-
By 7000 parts, be heated to the resol obtaining in the resistivity against fire particle (regeneration silica sand) of 130～140 ℃ and 105 parts of above-mentioned Production Examples 1～13 and drop into experiment with in sand muller, mixing 60 seconds.Next, add and make 23 parts of vulkacit Hs be dissolved in the solution forming in 105 parts of water, blow cooling, afterwards, add 7 parts of calcium stearates, obtain respectively shell mould RCS.
-evaluate-
According to above-mentioned test method, each RCS obtained above is carried out respectively to the mensuration of the mensuration of tar growing amount, the contractility of casting mold and coefficient of thermal expansion.Creating conditions of its result and resol is shown in following table 1 and table 2 in the lump.
[table 1]
[table 2]
From the result of above-mentioned table 1 and table 2, when RCS of the present invention is used the resol 1～10 of Production Example 1～10 to obtain, the growing amount of tar is few, and while coefficient of thermal expansion is low and contractility is large.On the other hand, utilize that the coefficient of thermal expansion of RCS of the resol 11 only use the Production Example 11 that phenol obtains is high and contractility is little.In addition, there is the problem that tar growing amount is many in the RCS of the resol 12 that utilization use phenol and dihydroxyphenyl propane obtain, and then, utilize to use the coefficient of thermal expansion of RCS of the resol 13 that hydrochloric acid obtains as catalysts and contractility to be inferior in performance to utilize and using the RCS of the resol 1 that obtains in the Production Example 1 of oxalic acid as catalysts.
Claims (6)
1. a shell mould coated sand, is characterized in that, uses shell mould to obtain with the coated resistivity against fire particle of resol, described shell mould resol is to use oxalic acid or use divalent metal salt and oxalic acid as catalyzer, make phenols and aphthols react and obtain with aldehydes, wherein
The ratio of described phenols and described aphthols is 95～50:5～50 by quality ratio; Described phenols (P) and aphthols (N) are 0.40～0.80 with mol ratio: the F/ (P+N) that reacts of described aldehydes (F);
Described phenols and aphthols with respect to amounting to 100 mass parts, used described catalyzer with the ratio of 0.01～5 mass parts;
With respect to the described resistivity against fire particle of 100 mass parts, use resol described in 0.2～10 mass parts.
2. shell mould coated sand as claimed in claim 1, is characterized in that, the described aphthols of described resol is 1-naphthols.
3. shell mould coated sand as claimed in claim 1, is characterized in that, the described aphthols of described resol is beta naphthal.
4. shell mould coated sand as claimed in claim 1, wherein, the number-average molecular weight of described resol is 400～1300.
5. shell mould coated sand as claimed in claim 1, wherein, described divalent metal salt is selected from lead naphthenate, zinc naphthenate, lead acetate, zinc acetate, zinc borate.
6. a casting mold, is that right to use requires the shell mould described in 1 to carry out moulding and it is heating and curing obtaining with coated sand.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-317113 | 2008-12-12 | ||
| JP2008317113 | 2008-12-12 | ||
| PCT/JP2009/006634 WO2010067562A1 (en) | 2008-12-12 | 2009-12-04 | Phenol resin for shell molding, process for production of the resin, resin-coated sand for shell molding, and molds obtained using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102245664A CN102245664A (en) | 2011-11-16 |
| CN102245664B true CN102245664B (en) | 2014-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200980149871.7A Active CN102245664B (en) | 2008-12-12 | 2009-12-04 | Phenol resin for shell molding, process for production of resin, resin-coated sand for shell molding, and molds obtained using same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110217554A1 (en) |
| JP (1) | JP5486510B2 (en) |
| KR (1) | KR20110104016A (en) |
| CN (1) | CN102245664B (en) |
| WO (1) | WO2010067562A1 (en) |
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|---|---|---|---|---|
| CN103613729B (en) * | 2013-12-16 | 2015-11-25 | 济南圣泉海沃斯树脂有限公司 | A kind of preparation method of modified phenolic resins |
| CN105348461A (en) * | 2015-12-29 | 2016-02-24 | 珠海市斗门福联造型材料实业有限公司 | Special high-strength modified phenolic resin adhesive for precoated sand and preparation method of special high-strength modified phenolic resin adhesive |
| CN110734543B (en) * | 2019-11-11 | 2022-04-29 | 煤炭科学技术研究院有限公司 | Naphthol modified phenolic resin and preparation method and application thereof |
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| JPH0578437A (en) * | 1991-09-18 | 1993-03-30 | Meiwa Kasei Kk | Phenolic novolak resin and curing agent for sealing semiconductor |
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| US9458349B2 (en) * | 2007-05-11 | 2016-10-04 | Georgia-Pacific Chemicals Llc | Phenol-formaldehyde novolac resin having low concentration of free phenol |
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- 2009-12-04 JP JP2010542001A patent/JP5486510B2/en active Active
- 2009-12-04 WO PCT/JP2009/006634 patent/WO2010067562A1/en active Application Filing
- 2009-12-04 CN CN200980149871.7A patent/CN102245664B/en active Active
- 2009-12-04 KR KR1020117015988A patent/KR20110104016A/en not_active Application Discontinuation
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2011
- 2011-05-13 US US13/106,948 patent/US20110217554A1/en not_active Abandoned
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| US5206333A (en) * | 1991-05-07 | 1993-04-27 | Hitachi Chemical Company, Ltd. | Method of producing a naphthol-modified phenolic resin of highly increased molecular weight |
| CN101291967A (en) * | 2005-10-27 | 2008-10-22 | 旭有机材工业株式会社 | Novolak type phenol resin for shell molding, method of producing the same and resin-coated sand |
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| Title |
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| JP特开平5-78437A 1993.03.30 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110104016A (en) | 2011-09-21 |
| JPWO2010067562A1 (en) | 2012-05-17 |
| CN102245664A (en) | 2011-11-16 |
| JP5486510B2 (en) | 2014-05-07 |
| WO2010067562A1 (en) | 2010-06-17 |
| US20110217554A1 (en) | 2011-09-08 |
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